Certificate of correction



United States Patent 2,993,742 PRINTING TEXTILE MATERIALS WITH VAT AND SULFUR DYESTUFFS Johannes Conrad, Ludwigshafen (Rhine), Alfons Jansen,

Ludwigshafen (Rhine)-0ppau, Heinz Weller and Adolf Blum, Ludwigshafen (Rhine), and Wilhelm Kueppers, Frankenthal (Pfalz), Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Aug. 26, 1958, Ser. No. 757,214 Claims priority, application Germany July 29, 1958 9 Claims. (Cl. 8-70) This invention relates to an indirect printing process with vat and sulfur dyestufis according to which a solution of a compound of the general formula:

-c--soi z in which E stands for an alkyl radical, G for a monovalent radical selected from the group consisting of a hydrogen atom and an alkyl radical, and Z for an alkali cation.

Processes for the printing of textile materials with vat and sulfur dyestuifs are known in which the dyestuff is printed on together with certain coagula-ble thickening agents, for example with alkylcellulose ethers, carob bean flour ethers, polyvinyl alcohol, ethers of gum guar, alginates or also simple carob bean flour thickenings. The printing pastes themselves contain no reducing agents, but now and again alkaline agents, such as potassium or sodium carbonate or also sodium hydroxide, depending on the compatibility of the thickenings with these alkaline agents. After printing and drying, the goods are treated with reducing agent solutions which may contain alkaline agents, and which usually contain additions which effect or promote the coagulation of the above-mentioned thickening agents, such as sodium borate or sodium aluminate, and in many cases also sodium sulfate. Sometimes these reducing agent solutions are thickened with non-coagulable thickeneing agents, such as tragacanth mucilage.

The textiles are supplied to a heat treatment immediately after the preparation, for example by means of a foulard or engraved rollers, and thus while still in the moist state and while excluding air. The reduction and fixation of the dyestuif is thus achieved. The heat transfer medium may be air-free saturated or superheated steam of l to 3 atmospheres absolute at a temperature of 100 to 200 C. Hot metal' baths or hot oil baths may however also be used, or hot water which if desired may be enriched with electrolytically-acting agents. The heat may furthermore be transferred to the moist textile material by hot metallic surfaces, the atmospheric oxygen being prevented from gaining access to the textile material by a preheated rubber cloth.

In all these methods, which are known under the names indirect printing with vat dyestuffs, vat pigment printing methods and two-phase printing methods, sodium formaldehyde sulfoxylate is chiefly used as the reducing agent, and more rarely sodium dithionite. These printing meth- "ree ods will hereinafter be referred to as two-phase printing methods or processes.

The advantage of sodium formaldehyde sulfoxylate solutions lies in the stability of these solutions at 20 C. and also in the fact that these solutions at 20 C. do not yet have a reducing action on vat dyestuffs. Thus even when padding the printed fabric webs in a foulard chassis, there does not occur either a vatting of the printed-on dyestuff (and consequent running of the color to the unprinted parts) or a soiling or tinting of the padding liquor. If with the development of the printed-on dyestufi it is also desired to achieve a coloring of the unprinted parts in pale shades, small amounts of vat and/or sulfur dyestuffs may be added to the sodium formaldehyde sulfoxylate solution.

It is a disadvantage, however, that when using sodium formaldehyde sulfoxylate as reducing agent, treatment periods of 3 to 5 minutes are necessary in the usual steamers, depending on the square meter weight of the textile web, in order to fix completely the printed-on dyestulf. It is true that when sodium dithionite is used as the reducing agent, shorter steaming periods of about 30 seconds duration are possible, but it is a disadvantage that sodium dithionite solutions reduce vat dyestuffs in the presence of alkali hydroxides and/or alkali carbonates even at 20 C. This leads to the printed-on vat dyestuffs vatting already in the foulard chassis during finishing, bleeding into the unprinted ground and the tinting or coloring in an undesirable way of the padding liquor or thickened sodium.

The instability of cold sodium dithionite solutions, even in the presence of alkaline agents, is also a disadvantage. When using sodium dithionite fixation, it is therefore necessary to prepare fresh padding liquors for the treatment of the fabric at short intervals of time, i.e. at intervals of 30 to minutes.

With this state of the art, a process is sought after which will combine the advantage of the reduction with sodium dithionite and the advantage of the reduction with sodium formaldehyde sulfoxylate without showing the disadvantages occasioned by the use of these reducing agents.

We have now found that textile materials can be printed in a specially advantageous way with dyestuffs selected from the group consisting of vat and sulfur dyestuffs by:

(1) Printing the material in a first stage with a dyestuff with the addition of a coagulable thickening agent and, after drying, fixing the prints in a second stage by in which E stands for an alkyl radical, G for a monovalent radical selected from the group consisting of a hydrogen atom and an alkyl radical and Z stands for analkali cation, and a subsequent short heat treatment,

(2) Printing the material in a first stage with a dyestuff with the addition of an alkaline agent and a coagulable thickening agent and, after drying, fixing the prints in a second stage by treatment with a solution of a compound of the general Formula I in which 'A, D, x, y and x+y have the above significance, and a subsequent short heat treatment, I

(3) Printing the material in a first stage with a dyestufi with the addition of a non-coagulable thickening agent and, after drying, fixing the prints in a second stage by spraying on a solution, containing an alkaline agent, of a compound of the general Formula I in which A, D, x, y, and x-I-y have the above significance, and a subsequent short heat treatment, or

(4) Printing the material in a first stage with a dyestuff with the addition of a alkaline agent and a non-coagulable thickening agent and fixing the prints in a second stage by spraying on a solution of a compound of the general Formula I in which A, D, x, y and x-l-y have the above significance, and a subsequent short heat treatment.

As low molecular weight alkyl radicals, such as straightchain or branched alkyl radicals, there are suitable for example the radicals of methane, ethane, propane and normal butane. One of the low molecular Weight alkyl radicals designated by A in Formula I above may in turn again bear a radical of the general formula:

(III) (file in which D has the above significance, p and -q are whole numbers from to 2 and p-l-q equal 2. Radicals of salts of alkylsulfinic acids with 2 to 4 carbon atoms of the general Formula II in which E, G and Z have the above specified meaning are for example'the radicals of sodium, potassium or ammonium salts of ethanesulfinic acid, propaue-l-sulfinic acid, propane-Z-sulfinic acid or normal butanesulfinic acid.

Compounds of the general Formula I in which A, D, x, y and x-l-y have the above specified meaning are obtained for example by replacing one or more of the hydrogen atoms attached to a nitrogen atom in ammonia or a primary or secondary low molecular weight amine, for example monoor di-amines, such as methylamine, dimethylamine, isopropylamine, normal-butylamine or ethylene diamine, by radicals of the Formula II in which E, G and Z have the above specified meaning. For example compounds of the general Formula I in which A, D, x, y and x-l-y have the above specified meaning may be obtained by allowing alkali salts of hydroxyalkylsulfinic acids with 2 to 4 carbon atoms which bear the hydroxyl group and the sulfinic acid group on the same carbon atom, for example the sodium, potassium or ammonium salts of l-hydroxyethanesulfinic acid-(l), l hydroxypropanesulfinic acid-(l), 2 hydroxypropanesulfinic acid-(2) or 1 hydroxy normal butanesulfinic acid-(l), to act on ammonia or primary or secondary low molecular weight aliphatic amines of the abovementioned kind. This reaction proceeds with the splitting off of water. Alkali salts of different hydroxyalkylsulfinic acids with 2 to 4 carbon atoms may also be allowed to act simultaneously or consecutively in any sequence on ammonia or on primary or secondary low molecular weight aliphatic amines of the above-mentioned kind.

The preparation of metal salts of hydroxy-alkyl sulfinic acids with 2 to 4 carbon atoms can be carried out by well known methods, e.g. by reaction of the corresponding aldehydes or ketones with metal hyposulfites, preferably sodium or zinc hyposulfites. See, for example, the preparation of sulfinic acids as disclosed by Gilman, Organic Chemistry, vol. I, pp. 913, 919, 2nd ed., John Wiley and Sons, 'Inc., New York (1949). The alkali salts ofthe hydroxy-alkyl sulfinic acids with12 to 4 carbon atoms can be obtained directly or by treatment of the calcium, barium, di-zinc or mono-zinc salts with aqueous solutions of alkali hydroxides or carbonates, for example, sodium or potassium hydroxide or carbonate, by so-called double decomposition.

As alkaline agents there may be mentioned for example sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate and/or mixtures of the same. Ascoagulable thickening agents there may be mentioned for example alkylcellulose ethers, carob bean 'fiour ether, polyvinyl alcohol, ethers of gum guar, algiuates or simple carobbean flour thickenings, and as non-coagulable thickening agents there may be mentioned for example tragacanth mucilage.

The term textile material should be understood as including structures, such as woven or knitted fabrics, especially those of native and/or regenerated cellulose, natural silk or linear polyamides. The fixation of the prints is efiected by a short heat treatment of 10 to 60 seconds duration at a temperature of to 200 C., advantageously between and C.

Solutions of compounds of the general Formula I in which A, D, x, y and x+y have the above specified meaning maybe obtained for example by dissolving the corresponding salts in water.

Such solutions may however also be obtained by socalled double decomposition from the analogous compounds which are present not as alkali salts but as salts diflicultly soluble in water, 'for example as calcium, barium or zinc salts, by treatment with aqueous solutions of alkali hydroxides or carbonates, for example sodium or potassium hydroxide or carbonate.

An advantage of the new process consists in the fact that the compounds of the general Formula I in which A, D, x, y and x-I-y have the above specified meaning, which-are used as reducing agents and which at ordinary temperature,.even in the presence of agents having a strongly alkaline reaction, such as sodium or potassium hydroxide, do not reduce vat dyestuffs and therefore do not effect any detachment of dyestufi in the padding liquor during the finishing of the printed fabric, have such a high speed of decomposition at temperatures above 50 C. that the dyestufi can be fixed on the fabric with a heat treatment equally as short as when using sodium dithionite as reducing agent. The new rapid fixing process also permits the :use of a far greater number of vat dyestufis than hitherto because when using sodium dithionite only those vat dyestuffs could be used which by reason of their high leuco dyestufi? potential are not reduced by cold sodium dithionite. The stability of aqueous solutions of the compounds of the general FormulaiI in which A, D, x, ,y .aridx-I-y have the-above specified meaning is so great against the oxygen and carbon dioxide content of the air even at 20 C. that the aqueous solutions can be sprayed onto the printed textile material without sufiering any appreciable loss of reducing agent. On the contrary if aqueous sodium dithionite solutions are sprayed, usually only between 5 and 30% of the reducing agent originally present can be detected in the solution collected. It is true that aqueous solutions of sodium =formaldehyde sulfoxylat can also be sprayed without appreciable loss of reductive power, but the use of this reducing agent is known to necessitate a much longer heat treatment for fixation of the dyestuff. -If,-on the contrary, the printed fabric is sprayed, as described, with aqueous solutions of compounds of the general Formula I in which A, D, x, y and x-l-y have the above specified meaning, it is possible on the :onehand to use. short heat treatment periods and on the other hand it is no longer "essential to use coagulable thickenings in the printing paste.

The followingexamples will further illustrate this invention but the invention is not restricted to these examples. The partsand percentages specified in the examplesare parts and-percentages by weight. i

1,000 parts.

After printing and drying, the fabric is finished with:

800 parts of water, 1 200 parts of a 30% aqueous solution of the compound of the formula N-omom-N Z 02S.HC 011.80: t i;

in which Z is a potassium cation and E a methyl p,

50 parts of sodium hydroxide and 5 parts of sodium metaborate.

The fabric while still moist is then exposed for 30 seconds to an air-free steam atmosphere at 108 C. without excess pressure. 1

To finish ofl the fabric it is treated for 2 minutes in flowing water at 20 C., 2 minutes in an aqueous solution at 95 C. which contains 2 grams of sodium perborate per liter, oxidized, soaped, rinsed and dried. A brilliant yellow print is obtained on a white ground.

The same result is achieved if, instead of being sub jected to the steaming process lasting 30 seconds, the prepared still moist fabric is applied to a metallic surface heated to 110 C. and covered with a rubber cloth preheated to about 80 C., this heat treatment lasting 25 seconds.

Instead of 200 parts of a 30% aqueous solution of the compound of the Formula IV in which Z is a potassium cation, there may also be used 200 parts of a 34% aqueous solution of the compound of the formula:

(V) $Hs CHn 69 )2 NCHt.CHsN H H in which Z is a potassium cation.

Example 2 A viscose rayon staple fiber fabric is printed with the following printing paste:

100 parts of a blue vat dyestutf, for example Vat Blue 14/01. 69810 (Color Index, 1956, volume 2, page 2501) in the form of a 15% aqueous paste,

50 parts of water,

600 parts of a 4.5% carob bean flour ether decoction in water,

200 parts of maize starch paste,

30 parts of potassium carbonate and 20 parts of sodium hydroxide 1,000 parts 6 After printing and drying, it' is treated with a solution of:

850 parts of water,

150 parts of a 40% aqueous solution of the compound of the Formula IV in which Z is a potassium cation and B an ethyl group, and

15 parts of sodium tetraborate.

Example 3 A cotton fabric is printed with the following printing paste:

100 parts of a yellow vat dyestufi, for example Vat Yellow 1/C.I. 70600 (Color Index, '195 6, volume 2, page 2427) in the form of a 20% queous paste,

150 parts of water,

500 parts of 6% tragacanth mucilage and 250 pants of a 10% wheat starch paste 1,000 parts.

The printed and dried fabric is sprayed with the following solution so that the fiabric takes up at least 50% of its own weight of solution:

800 parts of water, 200 parts of a 40% aqueous solution of the compound of the formula:

/N( lH.SO Loani in which Z is a sodium cation and E is a methyl group, and

50 parts of sodium hydroxide.

The still moist fabric is continuously supplied to a steamer and there treated for 30 seconds at about C. in air-free steam without excess pressure. The fabric is finished off according to Example 1.

A brilliant yellow print is obtained on a white ground.

Instead of 200 parts of a 40% aqueous solution of the compound of the Formula VI in which Z is a sodium cation and E a methyl group, there may also be used 200 parts of an aqueous 40% solution of the compound of the Formula VI in which Z is an ammonium cation and E a methyl group, or 200 parts of a 44% aqueous solution of the compound of the formula:

(VII) A cuprammonium rayon fabric is printed with the 'following paste:

30 .partsof a violet vat dyestufi, for exampleVat Vio- .let 1/.C;I. '60'01-0 (Color Index, .1956, volume 2, page 2479) 'in the'forrn ofa 15% aqueous pfaste, 220 parts of water, 500 parts of 6% tragacanth mucilage, 200 parts of a 10% wheat starch paste and 50 parts of-a30% British gumthickeniug (st-arch degraded by roasting) 1,00'0 par-ts. a 9

After printing and drying,.it.is sprayed with the following; solution in such a way that the fabrictakes up at least 50% of its own weight of solution:

800 parts of water 200 parts of a 35% aqueous solution of the compound of the Formula IV in which-.Z- is a sodium cation and E is a normal propyl radical,

SO partS-of sodiumihydroxide.

The still moist goods are continuously suppliedto "a steamer and there treated with air-free steam for 30 secondslat 110 C. The'finishing ofi'of the fabric takes place in the same way as described inExample 1.

The result is a brilliant red-violet printon a white ground.

The compound of the Formula IV in which '2 is a sodium cation 'a'ndE a normal propyl'radical may also be replaced by a compound of the formula:

VIII 1130 H3 e996 01st: ps0, nab 0H3 N-CHi.CH:-N z n HaC CH3 ozso ss0, Ha (BE:

in which Z is a sodium, potassium or ammonium cation.

Example A natural silk fabric is printed according to the following prescription:

40 parts of a green vat dyestuff, for example Vat Green l/C.I. 59855 (Color Index, 1956, volume 2, page 2519) in the form of a aqueous paste, 210 parts of water, 500 parts of a 5% -alkyl cellulose ether thickening'and 250 parts of a 10% wheat starch thickening.

1,000 parts.

After printing and drying, it is padded on the foulard with the following solution:

850 parts of water,

150 parts of a 30% aqueous solution of the compound of the Formula VTin which Z is a sodium cation and E amethyl group,

parts of sodium hydroxide and parts of potassium carbonate.

The still moist material is treated for .60 seconds at 0.3 atmosphereexcess pressure with air-free steam. The fur ther finishing oif takes place according to Example 1.

The result is a brilliant green print on a white ground.

The alkyl cellulose ether thickening may also be replaced by the same amount of a 17% polyvinyl alcohol thickening and instead of 1 5 0 parts of a aqueous solution of the compound o'fthe Formula VI in which is a sodium catiomand E a methyl group there may :8 also be used 150 parts of :a- .-39 aqueous solution of the compound of the-formulaz.

( H=C\ CH; 9

u-brnsoilm Example 6 A fabric of polycaprolactam fiber material is printed with thefollowingpaste:

40 parts of a green vat'dyestuff, for example Vat Green 1/C.I. 59855 (Color Index, 1956, volume 2;page 2519) in the form of a 10% aqueous paste, 1.10 parts of water, 600 parts of a 5% 'sodium-alginate thickening and 250 parts of a 10% wheat starch paste 1,000 parts.

After printing and drying it is padded w h the following solution one two-roller foulard:

800 Parts of water,

15 parts of aluminum sulfate (anhydrous),

45 parts of sodium hydroxide,

40 parts of sodiumoarbonate (calcined) "and 200' parts of a 40% solution of the compound of the Formula IV in which Z is a potassium atom and E a methyl group.

(X) CH3 S9 [oral-rt) 1 Ncim (Z99): I [1028.150 (13H:

in which Z 69 is a potassium cation. N I Example 7 A cotton fabric is printed with the following printing paste:

20 parts of a grey vat dyestuff, for example Vat Black 25/C.I. 69'525 (Color Index, 1956, volume 2, page 2560) in the form of a 20% aqueous paste,

parts of water, 600 parts of a 4.5% gurn guar ether decoction in water, 250 parts of a 10% wheat starch paste.

1,000 parts.

After printing and drying it is. padded with the following solution of a two-roller foulard:

850 parts of water,

parts of a 30% aqueous solution of the compound of the Formula VI in which Z is a potassium cation'and E a methyl group,

20 parts of sodium tetraborate and 50 parts of sodium hydroxide.

The still moist fabric is led through the following solution at 95 C. for the heat treatment:

730 parts of water,

200 parts of anhydrous sodium sulfate, 20 parts of sodium tetraborate and 20 parts of sodium hydroxide.

9. The treatment period in this solution lasts 40 seconds. The finishing off of the prints, such as oxidation, soaping and rinsing, takes place as in Example 1.

Grey prints are obtained on a white ground.

Example 8 A cotton fabric is printed with the following paste:

70 parts of a yellow vat dyestuif, for example Vat Yellow 2/C.I. 67300 (Color Index, 1956, volume 2, page 2428), in the form of a 20% aqueous paste,

30 parts of water,

600 parts of a 4.5% carob bean flour ether thickening,

and 300 parts of a wheat starch paste.

1,000 parts.

After printing and drying there is printed on by means of a roller engraved over the whole surface the following thickened reducing agent solution:

700 parts of Water,

100 parts of a 6% tragacanth mucilage,

200 parts of a 40% solution of the compound of the Formula IV in which Z is a sodium cation and E a methyl group, and

60 parts of sodium hydroxide.

The fabric is then treated for 35 seconds in air-free steam at 105 C. without the use of excess pressure. The finishing off of the prints takes place according to Example 1.

A brilliant greenish yellow print on a white ground is obtained.

The thickened reducing agent solution may have 1 to 3% of sodium tetraborate added thereto to coagulate the catch bean fluor ether thickening.

Example 9 A viscose rayon staple fiber fabric is printed with the following printing paste:

100 parts of a red vat dyestuflf, for example Vat Red 10/C.I. 67000 (Color Index, 1956, volume 2, page 2460) in the form of a aqueous paste,

50 parts of water, 600 parts of a 4.5% carob bean flour ether thickening,

and 250 parts of a 10% wheat starch paste.

1,000 parts.

The printed and dried fabric is prepared with the following reducing agent solution on a two-roller foulard:

750 parts of Water,

5 parts of a yellow vat dyestuif, for example Vat Yellow 1/C.I. 70600 (Color Index, 1956, volume 2, page 2427) in the form of a aqueous paste,

200 parts of a 40% solution of the compound of the Formula VI in which Z is a sodium cation and E a methyl group,

50 parts of sodium hydroxide and 15 parts of sodium tetraborate.

- The fabric is then treated for 30 seconds in air-free steam at 110 C. without excess pressure. The finishing oif of the steamed fabric is carried out as in Example 1.

A red print on a yellow ground is obtained.

The reducing agent solution containing vat dyestuif may also be thickened with 100 parts of a 6% tragacanth mucilage while omitting the same amount of water, and this thickened solution applied with a roller engraved over its whole surface.

1o Example 10 A white cotton fabric is printed according to the following prescription: 50 parts of a yellow sulfur dyestufi, for example C.I.- Sulfur Yellow 5 (Color Index, 1956, volume 2, page 2365), 15 parts of crystallized sodium sulfide, 135 parts of water, 600 parts of 6% tragacanth muscilage and 200 parts of 10% wheat starch paste.

1,000 parts.

After printing and drying, the fabric is sprayed with a solution of:

900 parts of water,

parts of a 40% aqueous solution of the compound of the Formula IV in which Z is a sodium cation and E a methyl group, and

50 parts of sodium hydroxide.

The still moist fabric is continuously supplied to a steamer and treated therein for 45 seconds in air-free steam at 110 C. The finishing off of the prints, such as oxidation, soaping and rinsing, takes place as in Example 1.

A yellow print is obtained on a white ground.

Instead of the said yellow sulfur dyestutf, there may also be used a brown sulfur dyestufi, for example C.I, Sulfur Brown 16/C.I. 53285 (Color Index, 1956, volume 2). In this case a deep brown print is obtained on a white ground.

Example 11 A white cotton fabric is printed with a printing paste according to Example 8 and dried. The following mixture is then prepared:

1,000 parts of water,

50 parts of sodium hydroxide,

15 parts of sodium tetraborate and 100 parts of the compound of the Formula VI in which Z is a zinc cation and E a methyl group.

After stirring round occasionally for 10 minutes, it is allowed to stand for 30minutes and the solution decanted from the sediment. During this time the corresponding sodium salt has formed from the zinc salt.

With the solution of the compound of the Formula VI in which Z 69 is a sodium cation and E a methyl group and containing sodium hydroxide and sodium tetraborate thus obtained-prepared from the compound of the Formula VI in which Z is a zinc cation and E a methyl group-the fabric is prepared on a two-roller foulard and then steamed for 20 seconds in air-free steam at C. The finishing off of the prints, such as oxidation, soaping and rinsing, takes place according to Example 1.

A yellow print is obtained on a white ground.

The prepared fabric may also be led over a steam heated drum in close contact with the surface thereof and the fabric protected from the action of atmospheric oxygen by covering it with a heat-stable elastic rubber or plastic cover. After a heat treatment of 20 seconds duration and a finishing off according to Example 1 the same result is achieved.

Example 1.2

caro b bean flour ether decoction with spasms 1 I Then a preparation solution is 'preparcd as follows:

1,000 parts of water,

20 parts of sodium hydroxide,

87 parts of the compound of the Formula 1V in which Z 69 is a'zinc cation andE a;methyl;.group, and

15 parts of sodium tetraborate.

After an occasional stirring lasting minutes'iand standing for another 30 minutes, the solution isdecanted from the sediment. A fabric prepared with this solution is treated for 30 seconds in air-free steam at 105 C. The finishing oil, such as oxidation, soaping and rinsing, takes place according to Example 1.

A violet print'is obtained onthe white fabric.

Example 13 A white cotton fabric is printed withtheflfollowing printing paste and dried:

30 parts of a violet vat dyestuiL't'or example Vat Violet 170.1.60010 (Color Index, 'l956,'volume 2, page 2479) in the' form of a 15% aqueous paste, 50 partsoi water,

700 parts of a 4.5% carob bean flour ether decoction in water and V 200 partsofa 10% wheatstarchpaste.

1,000 parts.

Then a preparation solution is prepared as follows:

900 parts of water 100 parts of potassium carbonate,

100 parts of the dr'fiiculty soluble'compound of the Formula VI in which. Z stands for /zCa and E'for a methyl group,

30 parts oi sodium hydroxide and 15 parts of sodium tetraborate.

The substances-are :added at intervals of 10 minutes to the water, with slight stirring. After standing for an hour, the solution is decanted firom the sediment. During this time, from the d-ifficultly soluble compound of the Formula VI in which Z stands for /z Ca and Bfor a methyl group, the readily soluble compound of the Formula VI inwhichZ stands for a potassium cation and E for a methyl group is formed, calcium-carbonate remaining-at the bottom ofthe vessel as-an insoluble precipitate. With the solution thus obtained, :the fabric is treated in a two-roller foulard and then steamedvfor 30 seconds in air-hee-steam at 110 C. The vfinishing oil, such as oxidation, soaping and rinsing takes 'place according to Example 1.

A violet print on a white ground is obtained.

Instead of the compounded the Formula VI in which Z for /2Ca and E stands for a -methyl group there may be added tothe above-mentionedpreparation solution the compound'of 'the'Formula VI in which Z stands for /zBa and 'E tor a methyl group, and the same result is achieved by maintaining the other working conditions.

We claim:

1. In a twophase printing process for printing textile materials with a dyestuff selected from the class consisting of vat dyestufis and sulfur dyestuffs wherein said textile material is treated in a firststage by printing thereon a composition containing said dyestuff and a thickening agent and thendrying said-textile material, and in a second stage by applying a reducing agent tosaid textile material and then heating for a short period of time sufiioient to fix said dyestuff on said textile material, .an alkaline agent also beingyapplied to-said textilematerial in at least one of said two stages, theimprovementwhich 12 comprises: :using as the: reducing 'agent in said second stage-a compound ot the general formula:

H wherein x represents a whole number from 0w 2, y represents a whole number from 1 to 3, x+y being equal to 3, A'represents a member selected from the group consisting of hydrogen, a lower molecular weight alkyl and when x equals 1 a lower molecular weight alkyl substituted by a radical of the general \Formula 'III below, and Drepresents the radical of a salt of an alkylsulfinic acid'with '2 to 4 carbon atoms of the general fior-mula (II) o-s0, z

in which Estands .for an alkyl radical, G stands for a memberselected from the group consisting of hydrogen and alkyl, and Z stands for an alkali ion, said substituent of the lower molecular weight alkyl designated by A above having the general formula: (III) (H),,

in which H is hydrogen, D has the same significance as set forth above and p and q each represent a whole number from 0 to 2, p+q being equal toZ.

2. An improved process as claimed in claim 1 wherein the textile material is heated in said second stage fora period of time of about 10 to 60 seconds at a temperature between..80 C. and 200 C.

3. An improved process as claimed in claim 2 wherein theheating-temperature is between about C.and C.

4. In a two-phase printing process for pn'ntingtextile materials with a dyestufi selected from the class consisting of vat dyestuffs and sulfur dyestuffs wherein said textile material is printed in a first stage with a composition containing said dyestuff and a coagulable thickening agent and then dried, and the print is fixed in a second stage by applying a solution,'containing an :alkaline agent, of a reducingagent and then heating for a period of time of about 10 to 60 seconds at atemperature between about 80 C. and 200 C., the improvement which comprises: employing as the reducing agent in said second stage a compound of the general formula:

whereiri'x represents: a whole number from Oato 2, y represents-a whole number from 1 to 3, x+y being equal to 3, A represents a member selected from the group consisting of hydrogen, a lower molecular weight alkyl and when equals 1 a lower molecular weight alkyl substituted by a radical of the general Formula 111 below, and vD represents the radical of a salt of an alkylsulfinic acid with 2 to 4 carbon atoms of the general formula in'whichiE stands for 'an alkyl radical, G standsfor a member selected from the group :consisting of hydrogen and alkyl, and Z stands for an alkali 'ion, said substituent of the lower molecular weight alkyl designated by A above having the general formula:

(III) n 13 in which H is hydrogen, D has the same significance as set forth above and p and q each represent a whole number from to 2, p-I-q being equal to 2.

5. In a two-phase printing process for printing textile materials with a dyestutf selected from the class consisting of vat dyestufis and sulfur dyestufis wherein said textile material is printed in a first stage with a composition containing said dyestufif, an alkaline agent and a coagulable thickening agent and then dried, and the print is fixed in a second stage by applying a solution of a reducing agent and then heating for a period of time of about to 60 seconds at a temperature between about 80 C. and 200 C., the improvement which comprises: employing as the reducing agent in said second stage a compound of the general formula:

wherein x represents a whole number from 0 to 2, y represents a whole number from 1 to 3, x-l-y being equal to 3, A represents a member selected from the group consisting of hydrogen, a lower molecular weight alkyl and when x equals 1 a lower molecular weight alkyl substituted by a radical .of the general Formula III below, and D represents the radical of a salt of an alkylsulfinic acid with 2 to 4 carbon atoms of the general formula (II) 1|:

in which E stands for an alkyl radical, G stands for a member selected from the group consisting of hydrogen and alkyl, and Z stands for an alkali ion, said snbstituent of the lower molecular weight alkyl designated by A above having the general formula:

in which H is hydrogen, D has the same significance as set forth above and p and q each represent a whole number from 0 to 2, p+q being equal to 2.

6. In a two-phase printing process for printing textile materials with a dyestuff selected from the class consisting of vat dyestuffs and sulfur dyestuffs wherein said textile material is printed in a first stage with a composition containing said dyestuif and a non-coagula-ble thickening agent and then dried, and the print is fixed in a second stage by applying a solution, containing an alkaline agent, of a reducing agent and then heating for a period of time of about 10 to 60 seconds at a temperature between about 80 C. and 200 C., the improvement which comprises: employing as the reducing agent in said second stage a compound of the general formula:

(III) wherein x represents a whole number from 0 to 2, y represents a whole number from 1 to 3, x-l-y being equal to 3, A represents a member selected from the group consisting of hydrogen, a lower molecular weight alkyl and when x equals 1 a lower molecular weight alkyl substituted by a radical of the general Formula HI below, and D represents the radical of a salt of an alkylsulfinic acid with 2 to 4 carbon atoms of the general formula in which E stands for an alkyl radical, G stands for a member selected from the group consisting of hydrogen and alkyl, and Z stands for an alkali ion, said substituent of the lower molecular weight alkyl designated by A above having the general formula:

(III) )p )q in which H is hydrogen, D has the same significance as set forth above and p and q each represent a whole number from 0 to 2, p+q being equal to 2.

7. In a two-phase printing process for printing textile materials with a dyestuff selected from the class consisting of vat dyestuffs and sulfur dyestuffs wherein said textile material is printed in a first stage with a composition containing said dyestuff, an alkaline agent and a noncoagulable thickening agent and then dried, and the print is fixed in a second stage by applying a solution of a reducing agent and then heating for a period of time of about 10 to 60 seconds at a temperature between about C. and 200 C., the improvement which comprises: employing as the reducing agent in said second stage a compound of the general formula: I

wherein x represents a whole number from 0 to 2, y represents a whole number from 1 to 3, x+y being equal to 3, A represents a member selected from the group consisting of hydrogen, a lower molecular weight alkyl and when x equals 1 a lower molecular weight alkyl substituted by a radical of the general Formula III below, and D represents the radical of a salt of an alkylsulfinic acid with 2 to 4 carbon atoms of the general formula in which E stands for an alkyl radical, G stands for a member selected from the group consisting of hydrogen and alkyl, and Z stands for an alkali ion, said substituent of the lower molecular weight alkyl designated by A above having the general formula:

)q in which H is hydrogen, D has the same significance as set forth above and p and q each represent a whole numher from 0 to 2, p+q being equal to 2.

8. An improved process as claimed in claim 4 wherein the reducing agent is prepared in situ in an aqueous solution employed in the second stage.

9. An improved process as claimed in claim 5 wherein the reducing agent is prepared in situ in an aqueous solution employed in the second stage.

References Cited in the file of this patent UNITED STATES PATENTS 2,164,930 Lubs July 4, 1939 2,276,704 Schneevoigt Mar. 17, 1942 2,315,514 Fox Apr. 6, 1943 2,412,909 Potter Dec. 17, 1946 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,993,742 July 25, 1961 d Letters Patent should read as corrected below.

Column 7, line 75, before "is a" insert Signed and sealed this 5th day of December 1961.

( SEA L) Attest:

ERNEST W. SWIDER Attesting Officer DAVID L. LADD Commissioner of Patents USCOMM-DC 

1. IN A TWO-PHASE PRINTING PROCESS FOR PRINTING TEXTILE MATERIALS WITH A DYESTUFF SELECTED FROM THE CLASS CONSISTING OF VAT DYESTUFFS AND SULFUR DYESTUFFS WHEREIN SAID TEXTILE MATERIAL IS TREATED IN A FIRST STAGE BY PRINTING THEREON A COMPOSITION CONTAINING SAID DYESTUFF AND A THICKENING AGENT AND THEN DRYING SAID TEXTILE MATERIAL, AND IN A SECOND STAGE BY APPLYING A REDUCING AGENT TO SAID TEXTILE MATERIAL AND THEN HEATING FOR A SHORT PERIOD OF TIME SUFFICIENT TO FIX SAID DYESTUFF ON SAID TEXTILE MATERIAL, AN ALKALINE AGENT ALSO BEING APPLIED TO SAID TEXTILE MATERIAL IN AT LEAST ONE OF SAID TWO STAGES, THE IMPROVEMENT WHICH COMPRISES: USING AS THE REDUCING AGENT IN SAID SECOND STAGE A COMPOUND OF THE GENERAL FORMULA: 